CN106757248B - The preparation facilities and method of lead dioxide electrode - Google Patents
The preparation facilities and method of lead dioxide electrode Download PDFInfo
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- CN106757248B CN106757248B CN201611068976.8A CN201611068976A CN106757248B CN 106757248 B CN106757248 B CN 106757248B CN 201611068976 A CN201611068976 A CN 201611068976A CN 106757248 B CN106757248 B CN 106757248B
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Abstract
The present invention provides a kind of preparation facilities of lead dioxide electrode and methods.The device includes electrolytic cell, anode network, POROUS TITANIUM and cathode plate；For containing electrolyte in electrolytic cell；Anode network is suspended on by anode tap in electrolytic cell, and is completely immersed in electrolyte, wherein the material for forming anode network is titanium, and is formed with tin-antimony oxide layer on the surface of anode network；POROUS TITANIUM, which is placed on anode network, is used as anode, and the surface of POROUS TITANIUM is formed with tin-antimony oxide layer, and POROUS TITANIUM is completely immersed in electrolyte；Cathode plate is suspended on by cathode leg in electrolytic cell, and the surface of the POROUS TITANIUM on the anode network and parallel with anode network, and cathode plate is completely immersed in electrolyte.The service life that the present invention can simplify production technology, improve the corrosion resistance of electrode and can extend electrode.
Description
Technical field
The present invention relates to brown lead oxide preparing technical field, more particularly to a kind of preparation facilities of lead dioxide electrode and
Method.
Background technology
Ti-supported lead dioxide electric pole is since it has good conductive property, high peroxide current potential, is not easy to be corroded, well
Electrocatalytic oxidation property and be widely used in electrolytic industry.Brown lead oxide is also used in proton exchange membrane (PEM) electrolysis
In slot, for generating ozone.
In the preparation of existing ti-supported lead dioxide electric pole, in order to avoid lead reacts and soaks titanium anode plate part
Enter in electrolyte, therefore, the surface of only subregion is coated with brown lead oxide on titanium anode plate, also, in preparation process, dioxy
Change lead to be difficult to be uniformly distributed in PEM electrolyzer on titanium anode plate, ti-supported lead dioxide electric is due to its compact structure, it is difficult to win
Appoint the porous requirement of gas-diffusion electrode.
Invention content
The present invention provides a kind of preparation facilities and method of lead dioxide electrode, can make a kind of porous titanium-based titanium dioxide
Lead electrode, directly applies to PEM electrolyzer, and simple production process lasts a long time.
In order to solve the above technical problems, one aspect of the present invention is：A kind of lead dioxide electrode is provided
Preparation facilities, the preparation facilities include：Electrolytic cell, anode network, POROUS TITANIUM and cathode plate；For containing electricity in the electrolytic cell
Solve liquid；The anode network is suspended on by anode tap in the electrolytic cell, and is completely immersed in the electrolyte, wherein shape
It is titanium at the material of the anode network, and tin-antimony oxide layer is formed on the surface of the anode network；The POROUS TITANIUM is placed in
It is used as anode, the surface of the POROUS TITANIUM to be formed with tin-antimony oxide layer on the anode network, the POROUS TITANIUM is completely immersed in institute
It states in electrolyte；The cathode plate is suspended on by cathode leg in the electrolytic cell, and porous on the anode network
The surface of titanium is simultaneously parallel with the anode network, and the cathode plate is completely immersed in the electrolyte.
Wherein, the POROUS TITANIUM is placed on the anode network, in the drop shadow spread of the cathode plate.
Wherein, the area of the anode network is more than the area of the cathode plate.
Wherein, the outer surface of the anode tap is formed with tin-antimony oxide layer.
Wherein, the surface of the anode tap is equipped with protective coating, to obstruct the anode tap and electrolyte.
Wherein, the porosity of the POROUS TITANIUM is 40%-60%.
In order to solve the above technical problems, another technical solution used in the present invention is：A kind of lead dioxide electrode is provided
Preparation method, this approach includes the following steps：POROUS TITANIUM is pre-processed, to form tin antimony oxygen on the POROUS TITANIUM surface
Compound layer；The POROUS TITANIUM is placed on an anode network, wherein form the material of the anode network as titanium, and the anode network
Surface be each formed with tin-antimony oxide layer；The anode network is hung on to the electrolytic cell for being loaded with electrolyte by anode tap
In, and the anode network and the POROUS TITANIUM is made to be completely immersed in the electrolyte；By cathode leg by a cathode hangs
In the electrolytic cell, makes the cathode hangs in the surface of the POROUS TITANIUM and keep the cathode plate parallel and the sun
Polar net, and the cathode plate is completely immersed in the electrolyte；It is powered to be electrolysed.
Wherein, the electrolyte includes：The lead nitrate solution of 0.5mol/L-1mol/L, the nitrate trihydrate of 15g/L-40g/L
The sodium fluoride that the nitric acid and mass fraction that copper, volume fraction are 0.3%-1% are 0.5%-1%.
Wherein, described the step of being powered to be electrolysed, includes：Using 30-50mA/cm2Current density electrolysis 3-
5min；Using 10-20mA/cm2Current density electrolysis 20-30min.
Wherein, described to pre-process POROUS TITANIUM, with the step of the POROUS TITANIUM surface forms tin-antimony oxide layer
Including：The POROUS TITANIUM surface is cleaned using hydrochloric acid；By four chlorinations of the POROUS TITANIUM immersion n-Butanol soluble cleaned
In tin and antimony trichloride mixed solution；The POROUS TITANIUM is taken out, and is dried；Calcination is carried out to the POROUS TITANIUM after drying；It is cold
But the POROUS TITANIUM after calcination.
The beneficial effects of the invention are as follows：The case where being different from the prior art, the present invention is by using POROUS TITANIUM as anode
To form brown lead oxide in POROUS TITANIUM, to form porous ti-supported lead dioxide electric pole, since anode network and POROUS TITANIUM are complete
Enter entirely in electrolyte and POROUS TITANIUM has many advantages, such as higher porosity and relatively advanced specific surface area, so as to make
Brown lead oxide is evenly distributed in POROUS TITANIUM surface, simplifies preparation process.Again due to POROUS TITANIUM be used as electrode matrix, with compared with
High porosity is conducive to dielectric transmission and circulation, improves electrode catalyst reaction speed.Meanwhile POROUS TITANIUM have compare
Flourishing specific surface area so that homogeneous current distribution can reduce the current density of electrode, improve the corrosion resistance of electrode, extend electricity
The service life of pole.
Description of the drawings
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, other are can also be obtained according to these attached drawings
Attached drawing.
Fig. 1 is a kind of structural schematic diagram of the preparation facilities of lead dioxide electrode provided in an embodiment of the present invention；
Fig. 2 is a kind of flow diagram of the preparation method of lead dioxide electrode provided in an embodiment of the present invention.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that the described embodiments are merely a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts all other
Embodiment shall fall within the protection scope of the present invention.
Referring to Fig. 1, Fig. 1 is a kind of structural representation of the preparation facilities of lead dioxide electrode provided in an embodiment of the present invention
Figure.
The preparation facilities of the lead dioxide electrode of the present embodiment includes electrolytic cell 10, anode network 20, POROUS TITANIUM 30 and the moon
Pole plate 40.Wherein, for containing electrolyte 11 in electrolytic cell 10.For example, electrolyte 11 includes：0.5mol/L-1mol/L
Lead nitrate solution, the nitrate trihydrate copper of 15g/L-40g/L, volume fraction be 0.3%-1% nitric acid and mass fraction be
The sodium fluoride of 0.5%-1%.
Anode network 20 is suspended on by anode tap 21 in electrolytic cell 10, and is completely immersed in electrolyte 11, wherein is formed
The material of anode network 20 is titanium, and is formed with tin-antimony oxide layer on the surface of anode network 20.POROUS TITANIUM 30 is placed in anode network 20
Upper that anode, the surface of POROUS TITANIUM 30 is used as to be formed with tin-antimony oxide layer, POROUS TITANIUM 30 is also completely into electrolyte 11.
Specifically, the size of the mesh of the anode network 20 of the present embodiment is 2*2cm, the porosity of POROUS TITANIUM 30 is
The size of 40%-60%, POROUS TITANIUM 30 are 3*3cm, thickness 1mm.In other embodiments, the mesh of anode network 20 can be with
It is other sizes, as long as POROUS TITANIUM 30 can be supported, it is to be understood that the mesh size of anode network 20 is got over
Greatly, more it can weaken the reaction occurred on anode network 20.The thickness of POROUS TITANIUM 30 is then smaller under the premise of proof strength get over
It is good.
Wherein, work of the tin-antimony oxide layer that the surface of POROUS TITANIUM 30 is formed in forming porous ti-supported lead dioxide electric pole
With including：
(1) high resistance titanium dioxide layer is prevented to be formed.Since tin-antimony oxide layer is on 30 surface of POROUS TITANIUM, electrolyte is difficult to
30 surface of POROUS TITANIUM is penetrated into, diffusion of the hydrone to porous Titanium base also has received blocking, so as to avoid titanium dioxide
It generates.
(2) interface resistance is reduced.Within the scope of certain Sb amounts, the conductivity of stannic oxide with the increase for mixing Sb amounts and by
It is cumulative big.
(3) enhancing β-PbO2Binding force between coating and porous Titanium base so that Ti/SnO2-SbOx/β-PbO2Electrode
Coating no longer occurs in process of anodic polarization to remove, and instead β-PbO2Homogeneous corrosion.
In the present embodiment, using POROUS TITANIUM 30 as anode, POROUS TITANIUM 30 has good electric conductivity, corrosion resistance, superior
Biocompatibility and the advantages that higher porosity.
POROUS TITANIUM 30 have higher porosity and larger specific surface area, be conducive to brown lead oxide dispersion and equably
It is formed in 30 surface of POROUS TITANIUM, also, the anode network 20 of the present invention is completely immersed in electrolyte, POROUS TITANIUM 30 thereon is also complete
It immerses in the electrolytic solution, thus brown lead oxide can be made to be evenly distributed in 30 surface of POROUS TITANIUM, preparation process is simple.Also, by
It is used as electrode matrix in POROUS TITANIUM 30, there is higher porosity, is conducive to dielectric transmission and circulation, improves electrode catalyst
Reaction speed.Meanwhile POROUS TITANIUM 30 has relatively advanced specific surface area so that homogeneous current distribution can reduce the electricity of electrode
Current density improves the corrosion resistance of electrolysis, extends the service life of electrode.
In addition, the present invention uses the anode network 20 of titanium matter, the corrosion of the electrolytic condition can be resisted.In the table of anode network 20
Face, which forms tin-antimony oxide, can increase Oxygen anodic evolution potential, avoid oxygen evolution, and otherwise reaction will all occur within anode network
On 20, and reactionless generation in POROUS TITANIUM 30.
Cathode plate 40 is suspended on by cathode leg 41 in electrolytic cell 10, and the POROUS TITANIUM 30 on anode network 20 is just
Top is simultaneously parallel with anode network 20, which is completely immersed in electrolyte 11.
Wherein, cathode plate 40 is equipped with multiple air holes 42, so that the gas that reaction generates is discharged in time.
By the way that electric current is connected between anode tap 21 and cathode leg 41 and provided for electric installation, anode and cathode is made to send out
Raw following reaction：
Anode：Pb2++2H2O-2e-→PbO2+4H+
Cathode：Cu2++2e-→Cu
Side reaction (is happened on cathode, but does not consume faradic currents)：3Cu+8HNO3→4H2O+3Cu(NO3)2+2NO↑
Wherein, anodic current efficiency is close to 100%.
In the present invention, since cathode plate 40 and anode network 20 are mutually parallel, and the distribution up and down in electrolytic cell 10, thus sun
There is no face cathode plates 40 for pole lead 21, to reduce the reaction on anode tap 21.
It is different from the prior art, the present invention is by using POROUS TITANIUM 30 as anode to form titanium dioxide in POROUS TITANIUM 30
Lead, to form porous ti-supported lead dioxide electric pole, since anode network 20 and POROUS TITANIUM 30 are completely into electrolyte 11, with
And POROUS TITANIUM 30 has many advantages, such as higher porosity and relatively advanced specific surface area, so as to make brown lead oxide equably divide
Cloth simplifies preparation process on 30 surface of POROUS TITANIUM.Again since POROUS TITANIUM 30 is used as electrode matrix, there is higher porosity,
Be conducive to dielectric transmission and circulation, improve electrode catalyst reaction speed.Meanwhile POROUS TITANIUM 30 compares table with relatively advanced
Area so that homogeneous current distribution can reduce the current density of electrode, improve the corrosion resistance of electrode, and extend electrode uses the longevity
Life.
In the present embodiment, POROUS TITANIUM 30 is placed on anode network 20, in the drop shadow spread of cathode plate 40, i.e. 40 face of cathode plate
Product can make the electric force lines distribution near anode surface more uniform slightly larger than the range of anode, mitigate edge effect.Anode network
20 area is more than the area of cathode plate 40, to facilitate the introducing of cathode plate.
In order to avoid anode tap 21 reacts, tin-antimony oxide layer is formed in the outer surface of anode tap 21.Or
Person can also set protective coating in some other embodiment on the surface of anode tap 21, to obstruct anode tap 21 and electricity
Liquid 11 is solved, is reacted to be further reduced anode tap 21.Specifically, protective coating can be PTFE.
The present invention also provides a kind of preparation methods of lead dioxide electrode, as shown in Fig. 2, Fig. 2 is the embodiment of the present invention
A kind of flow diagram of the preparation method of the lead dioxide electrode provided.This approach includes the following steps：
S11, POROUS TITANIUM is pre-processed, to form tin-antimony oxide layer on POROUS TITANIUM surface.
Specifically, the tin-antimony oxide layer on POROUS TITANIUM surface, which has, prevents high resistance titanium dioxide layer from being formed, reduces interface
Resistance and enhancing β-PbO2The effect of binding force between coating and Titanium base.
Pretreated step includes：
S111, POROUS TITANIUM surface is cleaned using hydrochloric acid.
In step S111, first the hydrochloric acid that volume ratio is 1: 3-1: 2 is boiled, to clean the dust and oil on POROUS TITANIUM surface
Dirt, while adjusting POROUS TITANIUM surface state.
S112, will be in the butter of tin and antimony trichloride mixed solution of the POROUS TITANIUM immersion n-Butanol soluble that cleaned.
Specifically, the mass fraction of butter of tin is 30%, the mass fraction of antimony trichloride is 10%.It is appreciated that
Ground, in other embodiments, the mass fraction of butter of tin and antimony trichloride can increase and decrease in proportion, and increase and decrease amplitude is 20%.
S113, POROUS TITANIUM is taken out, and dried.
The temperature of drying is 150-200 DEG C, and the present embodiment is 150 DEG C, and in this step, n-butanol can be evaporated, therefore
This step should be noted that stronger ventilation prevents from exploding.
S114, calcination is carried out to the POROUS TITANIUM after drying.
Wherein, the calcination temperature in step S114 is 450-500 DEG C, time 15-30min.For example, the present embodiment uses
500 DEG C of calcination 15min.
POROUS TITANIUM after S115, cooling calcination.
In the present embodiment, by POROUS TITANIUM cooling and then repetition step S114 and step S115, it is repeated 15 times.
S12, POROUS TITANIUM is placed on an anode network, wherein the material for forming anode network is titanium, and the surface of anode network is equal
It is formed with tin-antimony oxide layer.
The anode network of titanium matter can resist the corrosion of the electrolytic condition.Forming tin-antimony oxide on the surface of anode network can
Increase Oxygen anodic evolution potential, avoid oxygen evolution, otherwise reaction will all occur on anode network, and reactionless hair in POROUS TITANIUM
It is raw.
S13, anode network is hung in the electrolytic cell for being loaded with electrolyte by anode tap, and makes anode network and porous
Titanium is completely immersed in electrolyte.
Anode network and POROUS TITANIUM can be such that brown lead oxide is formed uniformly in POROUS TITANIUM completely into electrolyte.
Specifically, electrolyte include the lead nitrate solution of 0.5mol/L-1mol/L, 15g/L-40g/L nitrate trihydrate
The sodium fluoride that the nitric acid and mass fraction that copper, volume fraction are 0.3%-1% are 0.5%-1%.
Wherein, plumbi nitras is the source of the lead ion of electrode reaction.Copper ion bag body lead ion is deposited in cathode.
The addition of nitrate trihydrate copper so that cathode reaction becomes the deposition of copper from the deposition of lead, prevents lead excessive in cathode
Consumption, makes the concentration of lead ion in electrolyte be more prone to control, and the otherwise concentration variation of lead ion is understood extremely complex and is difficult to
Control.If not adding nitrate trihydrate copper, although still can determine the concentration variation of lead ion by many experiments, once
Condition control changes, and plumbum ion concentration will be different from experiment before.
Nitric acid prevents lead ion from hydrolyzing, and consume the metallic copper produced on cathode plate for adjusting pH.
Sodium fluoride prevents anode from generating oxygen, while improving brown lead oxide performance for improving analysis oxygen voltage.
In one embodiment, electrolyte includes the lead nitrate solution of 1mol/L, the nitrate trihydrate copper of 30g/L, volume point
The sodium fluoride that the nitric acid and mass fraction that number is 0.5% are 0.5%.
In another embodiment, electrolyte include the lead nitrate solution of 0.5mol/L, 15g/L nitrate trihydrate copper, body
The sodium fluoride that the nitric acid and mass fraction that fraction is 1% are 1%.
In yet another embodiment, electrolyte include the lead nitrate solution of 0.8mol/L, 35g/L nitrate trihydrate copper, body
The sodium fluoride that the nitric acid and mass fraction that fraction is 0.3% are 0.9%.
S14, by cathode leg by a cathode hangs in electrolytic cell, make cathode hangs in the surface of POROUS TITANIUM
And keep cathode plate parallel and anode network, and cathode plate is completely immersed in electrolyte.
Since anode tap does not have face cathode plate, thus the reaction on anode tap can be weakened.
S15, it is powered to be electrolysed.
The temperature of electrolytic process is 80 DEG C ± 5 DEG C, and temperature is excessively high to consume additional energy, and temperature is too low, can influence two
The performance of lead oxide.Voltage is 1.7V-1.9V, can specifically be controlled according to physical condition.Since the side reaction of electrolysis generates one
Nitrogen oxide, it is therefore desirable to pay attention to ventilation.
Step S15 includes using 30-50mA/cm2Current density electrolysis 3-5min, obtain α-PbO2, using 10-20mA/
cm2Current density electrolysis 20-30min, obtain β-PbO2。
For example, in one embodiment, step S15 first uses 40mA/cm2Current density electrolysis 5min, then use
20mA/cm2Current density electrolysis 30min.
In another embodiment, step S15 first uses 30mA/cm2Current density electrolysis 4min, then use 15mA/
cm2Current density electrolysis 20min.
In yet another embodiment, step S15 first uses 35mA/cm2Current density electrolysis 3min, then use 10mA/
cm2Current density electrolysis 30min.
After electrolysis stops, immediately by anode, i.e. POROUS TITANIUM is taken out, and rinses, drying.The side that POROUS TITANIUM faces cathode plate is
For required anode, it is not necessarily to other processing.
The metallic copper that cathode plate surface generates can be come back to the approach of side reaction in electrolyte, but side reaction is more cloudy
Pole, the rate of anode reaction are slow, thus after being electrolysed cathode surface still with the presence of a large amount of copper, so, be electrolysed end
Afterwards, cathode plate continues to impregnate in the electrolytic solution, and copper is made then to continue to dissolve.
It is noted that in electrolytic process, with the consumption of electrolyte, it is also necessary to replenishers, the present embodiment be added
Replenishers be lead oxide (yellow or red) and nitric acid, wherein the additive amount of replenishers is according to electrolysis dosage
Supplement is specially added consumption dosage according to side reaction consumption dosage, lead oxide and anode generates Rapid Dose Calculation.
For example, according to electrode reaction, 2mol nitric acid (reaction product of anode), 0.5mol metals are generated per 1mol electronics
The copper of copper (cathode reaction product), consumption 0.5mol lead ions (anode reaction consumption), generation consumes 4/3mol nitric acid (side reactions
Consumption), i.e., nitric acid generates 2/3mol only, and lead ion consumes 0.5mol only, without other consumption.
Electrolyte supplement, which is reacted, is：PbO+2HNO3→Pb(NO3)2+H2O
Therefore often supplement 1mol lead ions consume 2mol nitric acid and 1mol yellow lead oxides.
Therefore per 1mol electronics supplement 0.5mol yellow lead oxides and 1/3mol nitric acid.It is then by 1000 coulombs of electronics conversions
1.157 grams of yellow lead oxides and 1.524 grams of nitric acid (pure).
In conclusion the present invention can prepare the lead dioxide electrode that brown lead oxide is uniformly distributed on porous titanium-base,
The corrosion resistance that electrode can be improved extends the service life of electrode.
Mode the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this
Equivalent structure or equivalent flow shift made by description of the invention and accompanying drawing content, it is relevant to be applied directly or indirectly in other
Technical field is included within the scope of the present invention.
Claims (10)
1. a kind of preparation facilities of lead dioxide electrode, which is characterized in that including：Electrolytic cell, anode network, POROUS TITANIUM and tool are more
The cathode plate of a air hole；
For containing electrolyte in the electrolytic cell；
The anode network is suspended on by anode tap in the electrolytic cell, and is completely immersed in the electrolyte, wherein is formed
The material of the anode network is titanium, and is formed with tin-antimony oxide layer on the surface of the anode network；
The POROUS TITANIUM, which is placed on the anode network, is used as anode, and the surface of the POROUS TITANIUM is formed with tin-antimony oxide layer, institute
POROUS TITANIUM is stated to be completely immersed in the electrolyte；
The cathode plate is suspended on by cathode leg in the electrolytic cell, and the POROUS TITANIUM on the anode network just on
Anode network described in Fang Bingyu is parallel, and the cathode plate is completely immersed in the electrolyte.
2. preparation facilities according to claim 1, which is characterized in that the POROUS TITANIUM is placed on the anode network, institute
It states in the drop shadow spread of cathode plate.
3. preparation facilities according to claim 2, which is characterized in that the area of the anode network is more than the cathode plate
Area.
4. preparation facilities according to claim 3, which is characterized in that the outer surface of the anode tap is formed with tin antimony oxygen
Compound layer.
5. preparation facilities according to claim 3, which is characterized in that the surface of the anode tap is equipped with protective coating,
To obstruct the anode tap and electrolyte.
6. preparation facilities according to claim 1, which is characterized in that the porosity of the POROUS TITANIUM is 40%-60%.
7. a kind of preparation method of lead dioxide electrode, which is characterized in that including step：
POROUS TITANIUM is pre-processed, to form tin-antimony oxide layer on the POROUS TITANIUM surface；
The POROUS TITANIUM is placed on an anode network, wherein form the material of the anode network as titanium, and the table of the anode network
Face is each formed with tin-antimony oxide layer；
The anode network is hung in the electrolytic cell for being loaded with electrolyte by anode tap, and makes the anode network and described
POROUS TITANIUM is completely immersed in the electrolyte；
By cathode leg by a cathode hangs in the electrolytic cell, make the cathode hangs the POROUS TITANIUM just
Top simultaneously makes the cathode plate be parallel to the anode network, and the cathode plate is completely immersed in the electrolyte；
It is powered to be electrolysed.
8. preparation method according to claim 7, which is characterized in that the electrolyte includes：0.5mol/L-1mol/L's
The nitric acid and mass fraction that lead nitrate solution, the nitrate trihydrate copper of 15g/L-40g/L, volume fraction are 0.3%-1% is
The sodium fluoride of 0.5%-1%.
9. preparation method according to claim 8, which is characterized in that it is described energization to be electrolysed the step of include：
Using 30-50mA/cm2Current density electrolysis 3-5min；
Using 10-20mA/cm2Current density electrolysis 20-30min.
10. the method according to the description of claim 7 is characterized in that described pre-process POROUS TITANIUM, with described porous
Titanium surface formed tin-antimony oxide layer the step of include：
The POROUS TITANIUM surface is cleaned using hydrochloric acid；
It will be in the butter of tin and antimony trichloride mixed solution of the POROUS TITANIUM immersion n-Butanol soluble that cleaned；
The POROUS TITANIUM is taken out, and is dried；
Calcination is carried out to the POROUS TITANIUM after drying；
The POROUS TITANIUM after cooling calcination.
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